Transparent conductive film

ABSTRACT

Provided is a transparent conductive film including a transparent plastic film substrate and an indium-tin composite oxide transparent conductive film laminated on at least one surface of the transparent plastic film substrate, a value of the normalized integrated intensity of a diffraction peak measured by X-ray diffractometry in the (222) plane due to a crystal of the transparent conductive film being 4 to 25 cps⋅°/nm.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation application of U.S. application Ser. No.15/562,960, filed on Sep. 29, 2017, which is a 371 of PCT/JP2016/059171,filed on Mar. 23, 2016, which claims benefit of the filing date ofJapanese Patent Application No. 2016-012142, filed on Jan. 26, 2016, andJapanese Patent Application No. 2015-071243, filed on Mar. 31, 2015, thedisclosure of which is hereby incorporated in its entirety by reference.

TECHNICAL FIELD

The present invention relates to a transparent conductive film includinga transparent plastic film substrate and a crystalline indium-tincomposite oxide transparent conductive film laminated on the transparentplastic film substrate, particularly to a transparent conductive filmexcellent in pen sliding durability when used for a resistive film typetouch panel and in flexibility.

BACKGROUND ART

A transparent conductive film including a transparent plastic substrateand a transparent and low resistance thin film laminated on thetransparent plastic substrate has been widely used for application inelectric and electronic fields, such as application of utilizing theelectroconductivity of the film. e.g., a transparent electrode of, forexample, flat panel displays such as a liquid crystal display and anelectroluminescent (EL) display, and a touch panel.

A resistive film type touch panel includes in combination a fixedelectrode obtained by coating a glass or plastic substrate with atransparent conductive thin film and a movable electrode (filmelectrode) obtained by coating a plastic film with a transparentconductive thin film, and the resistive film type touch panel is used byoverlapping thereof on an upper side of a display body. The filmelectrode is pressed with a finger or a pen, so that the fixed electrodeand the transparent conductive thin film of the film electrode arebrought into contact with each other to serve as an input forrecognizing a position on the touch panel. In many cases, a pen appliesstronger force on the touch panel than a finger. Successive input on thetouch panel with a pen sometimes causes a rupture such as a crack orpeeling on the transparent conductive thin film on the film electrodeside. In addition, the transparent conductive thin film of the filmelectrode is sometimes broken at the time of bending the film electrode,for example, in a step of producing the touch panel or at the time of aninput at an end portion of the touch panel. This breaking in thetransparent conductive thin film is a phenomenon caused by insufficientflexibility of the transparent conductive thin film. In order to solvethese problems, a transparent conductive film is required that attainsboth excellent pen sliding durability and flexibility.

A means for increasing the pen sliding durability includes a method ofcrystallizing the transparent conductive thin film on the film electrodeside (for example, see PTD 1). In the conventional transparentconductive film, however, the crystallinity of an indium-tin compositeoxide is controlled to realize a transparent conductive film excellentin pen sliding durability. The conventional transparent conductive film,however, has been insufficient when subjected to the flexibility testdescribed below.

CITATION LIST Patent Document

PTD 1: Japanese Patent Laying-Open No. 2004-071171

SUMMARY OF INVENTION Technical Problems

An object of the present invention is to provide a transparentconductive film excellent in pen sliding durability when used for atouch panel and also in flexibility, in view of the conventional problemdescribed above.

Solutions to Problems

The present invention has been achieved in view of the circumstancesdescribed above, and a transparent conductive film of the presentinvention that has been capable of solving the above problem isconfigured as follows.

1. A transparent conductive film including a transparent plastic filmsubstrate and an indium-tin composite oxide transparent conductive filmlaminated on at least one surface of the transparent plastic filmsubstrate, a value of normalized integrated intensity of a diffractionpeak measured by X-ray diffractometry in a (222) plane due to a crystalof the transparent conductive film being 4 to 25 cps⋅°/nm.

2. The transparent conductive film according to 1, wherein theindium-tin composite oxide transparent conductive film has a crystalgrain size of 10 to 1000 nm.

3. The transparent conductive film according to 1 or 2, wherein theindium-tin composite oxide transparent conductive film includes 0.5 to10% by mass of tin oxide.

4. The transparent conductive film according to any one of 1 to 3,wherein the indium-tin composite oxide transparent conductive film has athickness of 10 to 30 nm.

Advantageous Effects of Invention

The present invention can provide a transparent conductive film that hasexcellent pen sliding durability and flexibility in combination. Aresultant transparent conductive film is very useful for applicationsuch as a resistive film type touch panel.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view illustrating one example (first example) ofthe longest part of a crystal grain in the present invention.

FIG. 2 is a schematic view illustrating another example (second example)of the longest part of a crystal grain in the present invention.

FIG. 3 is a schematic view illustrating another example (third example)of the longest part of a crystal grain in the present invention.

FIG. 4 is a schematic view illustrating another example (fourth example)of the longest part of a crystal grain in the present invention.

FIG. 5 is a schematic view for illustrating a position of a center rollin one example of a sputtering device suitably used in the presentinvention.

DESCRIPTION OF EMBODIMENT

A transparent conductive film of the present invention includes atransparent plastic film substrate and an indium-tin composite oxidetransparent conductive film laminated on at least one surface of thetransparent plastic film substrate, a value of the normalized integratedintensity of a diffraction peak measured by X-ray diffractometry in the(222) plane due to a crystal of the transparent conductive film beingpreferably 4 to 25 cps⋅°/nm.

The value of the normalized integrated intensity of a diffraction peakobserved by X-ray diffractometry in the (222) plane indicates the degreeof crystallinity of the indium-tin composite oxide transparentconductive film. The larger the value of the normalized integratedintensity of a diffraction peak is, the higher the crystallinity of theindium-tin composite oxide transparent conductive film is. Generally,the indium-tin composite oxide transparent conductive film high incrystallinity is hard, so that the transparent conductive film isexcellent in pen sliding durability but inferior in flexibility. In thetransparent conductive film of the present invention, the crystallinityis appropriately controlled to give a semi crystalline state describedbelow, thereby allowing the transparent conductive film to haveexcellent pen sliding durability and flexibility in combination.

Here, the X-ray diffractometry is described.

When a diffraction peak from an indium-tin composite oxide transparentconductive film laminated on a transparent plastic film is measured, itis often difficult to perform accurate measurement with a concentrationmethod optical system because of strong diffraction from the transparentplastic film. In many cases, the concentration method optical system canbe used for measurement when the transparent conductive film is high incrystallinity, for example. The transparent conductive film of PatentLiterature 1 can be measured with the concentration method opticalsystem and is therefore high in crystallinity. As regards thetransparent conductive film of the present invention, it is difficult toobserve a diffraction peak in the (222) plane with the concentrationmethod optical system. Therefore, a thin film method is used that is ameasuring method of allowing the X-ray to be incident with a veryshallow angle to the surface of a sample for restriction of penetrationdepth of the X-ray, to suppress as much influence as possible from thetransparent plastic film.

The value of the normalized integrated intensity of a diffraction peakin the (222) plane due to a crystal of the indium-tin composite oxidetransparent conductive film in the present invention is preferablygreater than or equal to 4 cps⋅°/nm, more preferably greater than orequal to 7 cps⋅°/nm. With the value of the normalized integratedintensity greater than or equal to 4 cps⋅°/nm, the crystallinity for thepen sliding durability is preferably not insufficient. On the otherhand, the value of the normalized integrated intensity of a diffractionpeak in the (222) plane due to a crystal of the indium-tin compositeoxide transparent conductive film is preferably less than or equal to 25cps⋅°/nm, more preferably less than or equal to 23 cps⋅°/nm. With thevalue of the normalized integrated intensity less than or equal to 25cps⋅°/nm, the crystallinity does not excessively increase, so that theflexibility is preferably retained.

The indium-tin composite oxide transparent conductive film of thepresent invention preferably has a crystal grain size of greater than orequal to 10 nm. The crystal grain size is more preferably greater thanor equal to 30 nm. With the crystal grain size greater than or equal to10 nm, the bonding power between crystal grains is retained topreferably easily satisfy the pen sliding durability. On the other hand,the indium-tin composite oxide transparent conductive film preferablyhas a crystal grain size of less than or equal to 1000 nm. The crystalgrain size is more preferably less than or equal to 500 nm. With thecrystal grain size less than or equal to 1000 nm, the flexibility ispreferably retained.

The transparent conductive film of the present invention includes anindium-tin composite oxide and preferably includes tin oxide in anamount of greater than or equal to 0.5% by mass and less than or equalto 10% by mass. Tin oxide in the indium-tin composite oxide is animpurity for indium oxide. The impurity tin oxide is contained to raisethe melting point of the indium-tin composite oxide. That is, inclusionof the impurity tin oxide serves to inhibit crystallization. Inclusionof tin oxide in an amount of greater than or equal to 0.5% by masspreferably brings the surface resistance of the transparent conductivefilm up to a practical level. The content rate of tin oxide is furtherpreferably greater than or equal to 1% by mass, particularly preferablygreater than or equal to 2% by mass. With the content rate of tin oxideless than or equal to 10% by mass, the crystallization in adjustment toform the semi crystalline state described below easily occurs topreferably improve the pen sliding durability. The content rate of tinoxide is more preferably less than or equal to 8% by mass, furtherpreferably less than or equal to 6% by mass, particularly preferablyless than or equal to 4% by mass. The transparent conductive film of thepresent invention preferably has a surface resistance of 50 to 900 Ω/□.

In the present invention, the transparent conductive film desirably hasa thickness of greater than or equal to 10 nm and less than or equal to30 nm. The transparent conductive film having a thickness of greaterthan or equal to 10 nm is not excessively amorphous and thus easilygives appropriate crystallinity for forming the semi crystalline statedescribed below, so that the pen sliding durability is preferablyretained, consequently. The thickness of the transparent conductive filmis more preferably greater than or equal to 13 nm, more preferablygreater than or equal to 16 nm. On the other hand, the transparentconductive film having a thickness of less than or equal to 30 nm is notexcessively crystalline and thus easily keep the semi crystalline state,so that the flexibility is preferably retained. The thickness of thetransparent conductive film is more preferably less than or equal to 26nm, further preferably less than or equal to 22 nm.

A production method for obtaining the transparent conductive film of thepresent invention is not particularly limited. The production method,however, can be exemplified as described below.

A sputtering method is preferably used as a method of forming thecrystalline indium-tin composite oxide transparent conductive film on atleast one surface of the transparent plastic film substrate. It isdesirable to form the transparent conductive film on the transparentplastic film by accurately controlling the ratio of the partial pressureof water to the partial pressure of an inert gas in an atmosphere duringsputtering so that the difference between the maximum value and theminimum value from the start to the completion of film formation becomesless than or equal to 2.0×10⁻⁴, and by keeping the temperature of thefilm less than or equal to 80° C. during film formation. The temperatureof the film during film formation is adjusted by using a settingtemperature of a temperature controller for adjusting the temperature ofa center roll in contact with the film that runs. Here, FIG. 5illustrates a schematic view of one example of a sputtering devicesuitably used in the present invention, and a film 1 that runs isrunning partially in contact with the surface of a center roll 2. Achimney 3 is installed between an indium-tin sputtering target 4 and thefilm 1, and a thin film of indium-tin composite oxide is deposited andlaminated on the surface of the film 1 traveling on the center roll 2.The temperature of center roll 2 is controlled by the temperaturecontroller (not illustrated). Examples of the inert gas include helium,neon, argon, krypton, and xenon. The central value (the intermediatevalue between the maximum value and the minimum value) in the ratio ofthe partial pressure of water to the partial pressure of the inert gasin the atmosphere during sputtering is desirably 4.0×10⁻⁴ to 2.9×10⁻³.The central value in the ratio of the partial pressure of water to thepartial pressure of the inert gas somewhat depends on the content rateof tin oxide in the indium-tin composite oxide transparent conductivefilm and the thickness of the transparent conductive film. When theamount of tin oxide added to the indium-tin composite oxide transparentconductive film is large or when the transparent conductive film isthin, it is desirable that the central value in the ratio of the partialpressure of water to the partial pressure of the inert gas be set low inthe range described above. Contrarily, when the content rate of tinoxide in the indium-tin composite oxide transparent conductive film islow or when the transparent conductive film is thick, it is desirablethat the central value in the ratio of the partial pressure of water tothe partial pressure of the inert gas be set high in the range describedabove. In addition, it is desirable to add an oxygen gas duringsputtering in order to bring the surface resistance and total lighttransmittance of the transparent conductive film up to a practicallevel.

The atmosphere for film formation largely including water is known todecrease the crystallinity of the transparent conductive film.Therefore, the amount of water in the atmosphere for film formation isan important factor. For control of the amount of water when theindium-tin composite oxide is formed into a film on the plastic film, itis desirable to actually observe the amount of water during filmformation. It is not preferable to use an ultimate vacuum for thecontrol of the amount of water in the atmosphere for film formationbecause of the following two reasons.

First, one of the reasons is that when the film is formed on the plasticfilm by sputtering, the film is heated to discharge moisture from thefilm, increasing the amount of water in the atmosphere for filmformation to increase the amount of water compared with when theultimate vacuum has been measured.

The second reason is applied to a case of a device that loads thetransparent plastic film in large amounts. Such a device loads the filmin a form of a film roll. A roll of film loaded into a vacuum chambereasily dehydrates on the outer layer portion of the roll, but is lesslikely to dehydrate on the inner layer portion of the roll. When theultimate vacuum is measured, the plastic film roll is stopped, but sincethe film roll runs during thin film formation and the inner layerportion of the plastic film roll containing a large amount of water isunwound, the amount of moisture in the atmosphere during sputteringincreases, and it increases more than the amount of moisture when theultimate vacuum is measured. In the present invention, it is possible topreferably control the amount of water in the atmosphere duringsputtering by observing the ratio of the partial pressure of water tothe partial pressure of the inert gas in the atmosphere duringsputtering.

The crystallinity of the transparent conductive film in the presentinvention is neither excessively high nor low (such crystallinity isreferred to as semi crystallinity or a semi crystalline property). It isvery difficult to stably make the transparent conductive film semicrystalline. This is because the semi crystallinity is a state wherecrystallization is stopped in middle of rapid phase transition fromamorphousness to crystallinity. Therefore, the process is very sensitiveto the amount of water in the atmosphere for film formation as aparameter involving the crystallinity, forming almost completecrystallinity (high crystallinity) when the amount of water is evenslightly short in the atmosphere for film formation and contrarilyforming amorphousness (low crystallinity) when the amount of water iseven slightly excessive in the atmosphere for film formation. Thus, inthe present invention, it is desirable to accurately control the ratioof the partial pressure of water to the partial pressure of the inertgas in the atmosphere during sputtering so that the difference betweenthe maximum value and the minimum value from the start to the completionof film formation becomes less than or equal to 2.0×10⁻⁴ in the methodof forming the indium-tin composite oxide transparent conductive film onat least one surface of the transparent plastic film substrate. With thedifference less than or equal to 2.0×10⁻⁴ between the maximum value andthe minimum value in the ratio of the partial pressure of water to thepartial pressure of the inert gas in the atmosphere during sputtering,the transparent conductive film is less likely to be formed to have amixture of a portion high in crystallinity and a portion low incrystallinity and easily becomes a transparent conductive film havinguniform semi crystallinity, so that it is possible to suitably give thetransparent conductive film that has excellent pen sliding durabilityand flexibility in combination.

As a method of accurately controlling the ratio of the partial pressureof water to the partial pressure of the inert gas in the atmosphereduring sputtering so that the difference between the maximum value andthe minimum value from the start to the completion of film formationbecomes less than or equal to 2.0×10⁻⁴, the following methods [1], [2],and [3] can be preferably employed, for example.

[1] Preferably employed is a method of introducing water into theatmosphere for film formation by a mass flow controller, continuouslyobserving by a gas analyzer the ratio of the partial pressure of waterto the partial pressure of the inert gas in the atmosphere duringsputtering, and feeding back the observation result of the partialpressure of water to the mass flow controller, to accurately control theratio of the partial pressure of water to the partial pressure of theinert gas in the atmosphere during sputtering so that the differencebetween the maximum value and the minimum value in the ratio becomesless than or equal to 2.0×10⁻⁴.

[2] Preferably employed is a method of introducing a hydrogenatom-containing gas (such as hydrogen, ammonia, or a mixed gas ofhydrogen and argon, this is not particularly limited as long as the gascontains a hydrogen atom) into the atmosphere for film formation by amass flow controller, continuously observing by a gas analyzer the ratioof the partial pressure of water to the partial pressure of the inertgas in the atmosphere during sputtering, and feeding back theobservation result of the partial pressure of water to the mass flowcontroller, to accurately control the ratio of the partial pressure ofwater to the partial pressure of the inert gas in the atmosphere duringsputtering so that the difference between the maximum value and theminimum value in the ratio becomes less than or equal to 2.0×10⁻⁴. Thehydrogen atom-containing gas is separated in the atmosphere duringsputtering to bond with, for example, oxygen in the atmosphere for filmformation to form water. Therefore, the addition of the hydrogenatom-containing gas has an equivalent effect to the addition of water.

[3] It is desirable that the ratio of the partial pressure of water tothe partial pressure of the inert gas in the atmosphere duringsputtering be always observed by a gas analyzer and the observationresult of the partial pressure of water be fed back to the temperatureof the center roll in contact with the transparent plastic film, toaccurately control the ratio of the partial pressure of water to thepartial pressure of the inert gas in the atmosphere during sputtering sothat the difference between the maximum value and the minimum value inthe ratio becomes less than or equal to 2.0×10⁻⁴. The transparentplastic film includes water, and therefore the amount of waterdischarged from the transparent plastic film can be controlled bychanging the temperature applied to the transparent plastic film. Forexample, the temperature of the center roll in contact with thetransparent plastic film may be increased for increasing the ratio ofthe partial pressure of water to the partial pressure of the inert gasin the atmosphere during sputtering. Contrarily, the temperature of thecenter roll in contact with the transparent plastic film may bedecreased for decreasing the ratio of the partial pressure of water tothe partial pressure of the inert gas in the atmosphere duringsputtering. The temperature of the transparent plastic film iscontrolled by using the temperature of a heating medium in thetemperature controller that controls the temperature of the center rollin contact with the transparent plastic film. In order to control theratio of the partial pressure of water to the partial pressure of theinert gas in the atmosphere during sputtering, it is desirable to use atemperature controller whose response speed to temperature is high.

As the method of accurately controlling the ratio of the partialpressure of water to the partial pressure of the inert gas in theatmosphere during sputtering so that the difference between the maximumvalue and the minimum value from the start to the completion of filmformation becomes less than or equal to 2.0×10⁻⁴, the methods [1], [2],and [3] above are preferable for the following reasons.

In order to produce the transparent conductive film in highproductivity, it is preferable to use the so-called roll type sputteringdevice that supplies a film roll and rolls up the film in a form of afilm roll after formation of a film. In order to improve theproductivity, a film roll of a long transparent plastic film is set inthe roll type sputtering device. In a step of forming the transparentconductive film by a sputtering method, the film roll easily dehydrateson the outer layer portion but is less likely to dehydrate on the innerlayer portion when the device inside is made into a substantially vacuumstate. Directly after the start of sputtering, the outer layer portionof the film roll is fed, and the amount of water discharged from thefilm fed is small, so that the amount of water discharged into theatmosphere for film formation is small. As the sputtering continues, thefilm is continuously fed from the film roll for running sequentiallyfrom the outer layer to the inner layer to feed the inner layer portionof the film roll that includes more water, increasing the amount ofwater in the atmosphere for film formation. In addition, the film isoften different in water content in the length-wise direction. In orderto stably make the transparent conductive film semi crystalline, it ispreferable to always monitor the amount of water and adjust the amountof water to an intended amount in prompt response to a detected changein the amount of water, because the amount of water in the atmospherefor film formation changes every moment. In the methods [1] and [2], themass flow controller is used, and therefore it is possible to adjust theamount of water to an intended amount in prompt response to a detectedchange in the amount of water. In the method [3] the temperaturecontroller high in response speed to temperature is used, and thereforeit is possible to adjust the amount of water to an intended amount inprompt response to a detected change in the amount of water.

In the method of forming the crystalline indium-tin composite oxidetransparent conductive film on at least one surface of the transparentplastic film substrate, it is desirable to form the transparentconductive film on the transparent plastic film by keeping thetemperature of the film during sputtering less than or equal to 80° C.The film having a temperature of less than or equal to 80° C. preventsgeneration of a large amount of water and an impurity gas such as anorganic gas from the film to desirably eliminate the possibility of afailure that the film slips with respect to the center roll.

In the method of forming the crystalline indium-tin composite oxidetransparent conductive film on at least one surface of the transparentplastic film substrate, the central value in the ratio of the partialpressure of water to the partial pressure of the inert gas (theintermediate value between the maximum value and the minimum value fromthe start to the completion of film formation) in the atmosphere duringsputtering is desirably 4.0×10⁻⁴ to 3.0×10⁻³. With the central value inthe ratio of the partial pressure of water to the partial pressure ofthe inert gas greater than or equal to 4.0×10⁻⁴, the crystallinity ofthe transparent conductive film does not excessively increase, so thatthe flexibility is preferably retained. With the central value in theratio of the partial pressure of water to the partial pressure of theinert gas less than or equal to 3.0×10⁻³, the crystallinity of thetransparent conductive film does not excessively decrease, so that thepen sliding durability is preferably retained. The central value in theratio of the partial pressure of water to the partial pressure of theinert gas also depends on the amount of tin oxide added to theindium-tin composite oxide transparent conductive film and the thicknessof the transparent conductive film. When the amount of tin oxide addedto the indium-tin composite oxide transparent conductive film is largeor when the transparent conductive film is thin, it is desirable thatthe central value in the ratio of the partial pressure of water to thepartial pressure of the inert gas be set low in the range describedabove. Contrarily, when the amount of tin oxide added to the indium-tincomposite oxide transparent conductive film is low or when thetransparent conductive film is thick, it is desirable that the centralvalue in the ratio of the partial pressure of water to the partialpressure of the inert gas be set high in the range described above.

In the method of forming the crystalline indium-tin composite oxidetransparent conductive film on at least one surface of the transparentplastic film substrate, it is desirable to introduce an oxygen gasduring sputtering. The introduction of an oxygen gas during sputteringpreferably eliminates a failure caused by a lack of oxygen in theindium-tin composite oxide transparent conductive film, lowers thesurface resistance of the transparent conductive film, and increases thetotal light transmittance. Therefore, it is desirable to introduce anoxygen gas during sputtering in order to bring the surface resistanceand total light transmittance of the transparent conductive film up to apractical level.

The transparent conductive film of the present invention preferably hasa total light transmittance of 70 to 95%.

The transparent conductive film of the present invention is desirablyformed through a heating treatment in an atmosphere including oxygen at80 to 200° C. for 0.1 to 12 hours after the indium-tin composite oxidetransparent conductive film is formed and laminated on the transparentplastic film substrate. With the temperature greater than or equal to80° C., a treatment of slightly increasing the crystallinity for forminga semi crystalline state is easy to preferably increase the pen slidingdurability. With the temperature less than or equal to 200° C., theflatness of the transparent plastic film is preferably secured.

<Transparent Plastic Film Substrate>

The transparent plastic film substrate used in the present invention isa film obtained by subjecting an organic polymer to melt extrusion orsolution extrusion to form a film and subjecting the resultant film, asnecessary, to drawing in the length-wise direction and/or the width-wisedirection, cooling, and heat setting. Examples of the organic polymerinclude polyethylene, polypropylene, polyethylene terephthalate,polyethylene-2,6-naphthalate, polypropylene terephthalate, nylon 6,nylon 4, nylon 66, nylon 12, a polyimide, a polyamide-imide,polyethersulfone, polyetheretherketone, polycarbonate, polyarylate,cellulose propionate, polyvinyl chloride, polyvinylidene chloride,polyvinyl alcohol, polyether imide, polyphenylene sulfide, polyphenyleneoxide, polystyrene, syndiotactic polystyrene, and a norbornene polymer.

Among these organic polymers, preferred are, for example, polyethyleneterephthalate, polypropylene terephthalate,polyethylene-2,6-naphthalate, syndiotactic polystyrene, a norbornenepolymer, polycarbonate, and polyarylate. These organic polymers may becopolymerized with a monomer of another organic polymer in a smallamount or blended with another organic polymer.

The transparent plastic film substrate used in the present invention hasa thickness ranging preferably from 10 to 300 μm, particularlypreferably from 70 to 260 μm. The plastic film having a thickness ofgreater than or equal to 10 μm is preferable from the viewpoint ofdurability because the mechanical strength is retained to be small indistortion against an input with a pen when the plastic film substrateis used particularly for a touch panel. On the other hand, thetransparent plastic film substrate having a thickness of less than orequal to 300 μm is preferable because it is unnecessary to particularlyincrease a load for recognition of a position by an input with a penwhen the transparent plastic film substrate is used for a touch panel.

The transparent plastic film substrate used in the present invention maybe subjected to a surface activation treatment such as a coronadischarge treatment, a glow discharge treatment, a flame treatment, anultraviolet radiation treatment, an electron beam radiation treatment,or ozonation without impairing the purpose of the present invention.

An effect of increasing the pen sliding durability can be expected whenthe transparent plastic film substrate is coated with a curable resinlayer a surface of which is made into projections and recesses and thenthe transparent conductive film is formed on the projections andrecesses. The effect includes two main points. The first point is thatthe adhesion force between the transparent conductive thin film and thecurable resin layer is increased to prevent peeling of the transparentconductive film caused by sliding of a pen, increasing the pen slidingdurability. The second point is that an actual contact area decreasesthat is made when sliding of a pen brings the transparent conductivethin film into contact with glass, to improve the slidability between aglass surface and the transparent conductive film, increasing the pensliding durability. The curable resin layer will be described in detailbelow.

<Curable Resin Layer>

The curable resin preferably used in the present invention is notparticularly limited as long as it is a resin cured by application ofenergy such as heating, irradiation with ultraviolet, or irradiationwith an electron beam, and examples of the curable resin include asilicone resin, an acrylic resin, a methacrylic resin, an epoxy resin, amelamine resin, a polyester resin, and a urethane resin. From theviewpoint of productivity, an ultraviolet curable resin is preferablycontained as a main component.

Examples of such an ultraviolet curable resin can include polyfunctionalacrylate resin such as acrylic acid (ester) or methacrylic acid ester ofpolyhydric alcohol; and polyfunctional urethane acrylate resinssynthesized from diisocyanates, polyhydric alcohols, and hydroxyalkylesters of acrylic acid or methacrylic acid. A monofunctional monomersuch as vinylpyrrolidone, methylmethacrylate, or styrene can be added tothese polyfunctional resins for copolymerization as necessary.

In order to increase the adhesion force between the transparentconductive thin film and the curable resin layer, it is effective totreat a surface of the curable resin layer by the following techniques.Specific examples of the techniques include a discharge treatment methodof irradiating the surface by glow or corona discharge to increase acarbonyl group, a carboxyl group, and a hydroxyl group, and a chemicalagent treatment method of treating the surface with an acid or an alkalito increase polar groups such as an amino group, a hydroxyl group, and acarbonyl group.

For the use of the ultraviolet curable resin, a photoinitiator isusually added. As the photoinitiator, a known compound that absorbsultraviolet and generates a radical can be used without any particularlimitation, and examples of such a photoinitiator include variousbenzoins, phenylketones, and benzophenones. It is preferable to usuallyset the amount of the photoinitiator added to the ultraviolet curableresin to 1 to 5 parts by mass per 100 parts by mass of the ultravioletcurable resin.

In the present invention, the curable resin layer preferably contains,in addition to the main constituent curable resin, a resinnon-compatible with the curable resin in combination. The combinationuse of a small amount of resin non-compatible with the matrix curableresin can cause phase separation in the curable resin to disperse thenon-compatible resin in a particle state. These dispersed particles ofthe non-compatible resin can form projections and recesses on a surfaceof the curable resin to increase the surface roughness in a wide region.

When the curable resin is the ultraviolet curable resin, examples of thenon-compatible resin include a polyester resin, a polyolefin resin, apolystyrene resin, and a polyamide resin.

In the present invention, when the ultraviolet curable resin is used asthe main constituent curable resin of the curable resin layer and a highmolecular weight polyester resin is used as the polymer resinnon-compatible with the curable resin, the polyester resin is blended ina ratio of preferably 0.1 to 20 parts by mass, further preferably 0.2 to10 parts by mass, particularly preferably 0.5 to 5 parts by mass, to 100parts by mass of the ultraviolet curable resin.

With the polyester resin having a blending amount of greater than orequal to 0.1 parts by mass per 100 parts by mass of the ultravioletcurable resin, the projections formed on the surface of the curableresin layer are not excessively small to effectively impart the surfaceroughness, preferably giving an effect of further improving the pensliding durability. On the other hand, with the polyester resin having ablending amount of less than or equal to 20 parts by mass per 100 partsby mass of the ultraviolet curable resin, the curable resin layerpreferably retains chemical resistance as well as strength.

The polyester resin, however, is sometimes less preferable because thedifference in refractive index between the polyester resin and theultraviolet curable resin tends to increase a haze value of the curableresin layer and decrease the transparency of the curable resin layer.The high molecular weight polyester resin can also preferably be used asan antiglare film having a high haze value and thus having an antiglarefunction by contrarily, in a positive manner, using the deterioration intransparency caused by dispersed particles of the polyester resin.

Each of the ultraviolet curable resin, the photoinitiator, and the highmolecular weight polyester resin is dissolved in a common solvent toprepare a coating solution. The solvent used is not particularlylimited, and examples of the solvent include alcohol solvents such asethyl alcohol and isopropyl alcohol, ester solvents such as ethylacetate and butyl acetate, ether solvents such as dibutyl ether andethylene glycol monoethyl ether, ketone solvents such as methyl isobutylketone and cyclohexanone, and aromatic hydrocarbon solvents such astoluene, xylene, and solvent naphtha. These solvents can be used singlyor in mixture.

The concentration of the resin components in the coating solution can beappropriately selected in consideration of, for example, viscositysuitable for a coating method. For example, the total amount of theultraviolet curable resin, the photoinitiator, and the high molecularweight polyester resin usually accounts for 20 to 80% by mass of thecoating solution. This coating solution may also contain, as necessary,other known additives such as a silicone leveling agent.

In the present invention, the transparent plastic film substrate iscoated with the coating solution prepared. A coating method is notparticularly limited, and a conventionally know method can be used, suchas a bar coating method, a gravure coating method, or a reverse coatingmethod.

The coating solution applied is subjected to a next drying step wherethe solvent is removed by evaporation. In this step, the high molecularweight polyester resin that has been uniformly dissolved in the coatingsolution is formed into fine particles and precipitated in theultraviolet curable resin. The resultant coating layer is dried and theplastic film is irradiated with ultraviolet to cross-link and cure theultraviolet curable resin to form the curable resin layer. In thiscuring step, the fine particles of the high molecular weight polyesterresin are fixed into the hard coat layer and form protrusions on thesurface of the curable resin layer to increase the surface roughness ina wide region.

The curable resin layer preferably has a thickness ranging from 0.1 to15 μm. The thickness ranges more preferably from 0.5 to 10 μm,particularly preferably from 1 to 8 μm. With the curable resin layerhaving a thickness of greater than or equal to 0.1 μm, sufficientprotrusions are preferably formed. On the other hand, with the curableresin layer having a thickness of less than or equal to 15 μm, theproductivity is preferably good.

EXAMPLES

The present invention will be described in further detail below withreference to examples. Any part of the present invention, however, isnot limited by these examples. Various measurement evaluations in theexamples were performed by the following methods.

(1) Total Light Transmittance

The total light transmittance was measured with use of NDH-2000manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD. in accordance withJIS-K7136.

(2) Surface Resistance Value

The measurement was performed by a four-terminal method in accordancewith JIS-K7194. Used as a measurement device was Loresta AX MCP-T370manufactured by Mitsubishi Chemical Analytech, Co., Ltd.

(3) Value of normalized integrated intensity of diffraction peak in(222) plane

As regards the transparent conductive film of the present invention, itwas difficult to observe a diffraction peak in the (222) plane with aconcentration method optical system. Therefore, a thin film method wasused that was a measuring method of allowing the X-ray to be incidentwith a very shallow angle to the surface of a sample for restriction ofpenetration depth of the X-ray, to suppress as much influence aspossible from the transparent plastic film.

The measurement was performed with use of the samplehorizontally-holding X-ray diffractometer for thin film evaluation SmartLab manufactured by Rigaku Corporation as an X-ray diffractometer. Aparallel beam optical system including a multilayer film mirror was usedand a CuKα ray (wavelength: 1.54186 angstroms) was used as a lightsource with an output of 40 kV and 30 mA. Used as an incidence-end slitsystem was a soller slit (5.0°), an incident slit (0.2 mm), and alongitudinal control slit (10 mm), and used as a receiving-end slit wasa parallel slit analyzer (PSA) (0.114 deg). A 20-mm square sample may befixed to a stage with double sided tape or fixed by suction with use ofa porous suction sample holder. The measurement was performed at anincident angle of the X-ray of 0.25°, with a scintillation counterdetector scanned in an out-of-plane direction, and at a step interval of0.02° and a measurement speed of 2.0°/min. A diffraction line from the(222) plane of an ITO film appears at a position of about 30.5° (2θ) asa peak when a CuKα ray is used. Background subtraction was performedaccording to the Sonneveld-Visser method (Sonneveld. E. J. & Visser, J.W., J. Appl. Cryst. 8, 1 (1975)) and the integrated intensity of adiffraction peak in the (222) plane was calculated. A value obtained bydividing the integrated intensity by the thickness of the transparentconductive film is defined as a value of the normalized integratedintensity of the diffraction peak in the (222) plane. The thickness ofthe transparent conductive film was obtained by the method described in“(5) Thickness of transparent conductive film (film thickness)” below.

(4) Crystal Grain Size

A film specimen obtained by laminating the transparent conductive thinfilm layer was cut out into a size of 1 mm×10 mm and attached to anupper surface of an appropriate resin block with the surface of theconductive thin film directed outside. After the film specimen wastrimmed, an ultra-thin piece approximately parallel to the film surfacewas prepared by a general technical method of ultra microtome.

This piece was observed with a transmission electron microscope(JEM-2010 manufactured by JEOL Ltd.) to select a conductive thin filmpart that had no remarkable damage, and the part was photographed with adirect magnification of 40000 times by accelerating voltage of 200 kV.

All the crystal grains observed under the transmission electronmicroscope are measured for their longest parts and the average value oftheir measurement values is defined as a crystal grain size. Here, FIGS.1 to 4 illustrate examples involving a method of identifying the longestpart in the measurement of the maximum length of a crystal grain. Thatis, the longest part is identified by the length of a straight line thatcan be measured as the longest grain size of a crystal grain.

(5) Thickness of Transparent Conductive Film (Film Thickness)

A film specimen obtained by laminating the transparent conductive thinfilm layer was cut out into a size of 1 mm×10 mm and embedded in anepoxy resin for an electron microscope. The embedded specimen was fixedto a sample holder of an ultra microtome and a cross-sectional thinpiece was prepared that is parallel with a short side of the specimenembedded. Next, this piece was photographed at a portion that had noremarkable damage of the thin film with a transmission electronmicroscope (JEM-2010 manufactured by JEOL Ltd.) at an acceleratingvoltage of 200 kV and an observation magnification of 10000 times in abright field, and the film thickness was measured from the photographobtained.

(6) Pen Sliding Durability Test

The transparent conductive film was used as one panel plate, and used asthe other panel plate was a transparent conductive thin film (S500,manufactured by Nippon Soda Co., Ltd.) that included a glass substrateand a 20-nm thick indium-tin composite oxide thin film (tin oxidecontent: 10% by mass) laminated on the glass substrate by a plasma CVDmethod. These two panel plates were disposed so as to face theirtransparent conductive thin films with epoxy beads having a diameter of30 μm interposed between the panel plates to prepare a touch panel.Next, the touch panel was subjected to a 150000 reciprocal linearsliding test with a load of 2.5 N applied to a polyacetal pen (tipshape: 0.8 mm R). In the test, the sliding distance was 30 mm and thesliding speed was 180 mm/s. After this sliding durability test, first,the sliding portion was visually observed to confirm whether or not itwas whitened. Further, an ON-resistance (resistance value when a movableelectrode (film electrode) was brought into contact with a fixedelectrode) was measured with the sliding portion pressed with a pen loadof 0.8 N. The ON-resistance is desirably less than or equal to 10 kΩ.

(7) Flexibility Test

The transparent conductive film was cut into a rectangular shape havinga size of 20 mm×80 mm. Next, the rectangular-shaped transparentconductive film was measured for its resistance value with the shortsides of the rectangle joined with a tester. The transparent conductivefilm was bent with its transparent conductive film directed outside, andthe bending diameter of the transparent conductive film was recordedwhen the resistance value of the tester started to increase. The bendingdiameter is desirably less than or equal to 15.5 mm.

(8) Measurement of Content Rate of Tin Oxide in Transparent ConductiveFilm

A sample (about 15 cm²) was cut out and put in a quartz conical flask,20 ml of 6 mol/l hydrochloric acid was added to the flask, and the flaskwas sealed with a film to prevent volatilization of the acid. The flaskwas sometimes shaken at room temperature and left to stand for 9 days todissolve the ITO layer. The remaining film was taken out and thehydrochloric acid having the ITO layer dissolved therein was used as ameasurement solution. The content rates of In and Sn in the dissolutionsolution were measured by a calibration curve method with use of aninductively coupled plasma (ICP) emission analyzer (maker: RigakuCorporation, model: CIROS-120 EOP). As a measurement wavelength for eachelement, a non-interference and highly sensitive wavelength wasselected. As standard solutions, commercially available standardsolutions of In and Sn were used after diluted.

Each of the transparent plastic film substrates used in the examples andcomparative examples is a biaxially oriented transparent PET film havingan easily adhering layer on both surfaces thereof (A4340, manufacturedby TOYOBO CO., LTD., thickness 188 μm). As the curable resin layer, acoating solution was prepared by blending 3 parts by mass of a copolymerpolyester resin (VYLON 200, manufactured by TOYOBO CO., LTD., weightaverage molecular weight 18,000) with 100 parts by mass of aphotoinitiator-containing acrylic resin (SEIKABEAM (registered tradename) EXF-01J, manufactured by Dainichiseika Color & Chemicals Mfg. Co.,Ltd.), adding, as a solvent, a mixed solvent of toluene/MEK (8/2: ratioby mass) so that the solid content concentration became 50% by mass, andstirring the resultant solution for uniform dissolution (this coatingsolution is hereinafter referred to as a coating solution A). Thetransparent plastic film substrate was coated with the prepared coatingsolution with a Meyer bar so that the thickness of a coating layerbecame 5 μm. The coating layer was dried at 80° C. for 1 minute andirradiated with ultraviolet (light quantity: 300 mJ/cm²) by anultraviolet radiation device (UB042-5AM-W model, manufactured by EYEGRAPHICS CO., LTD.) to cure the coating layer.

Examples 1 to 9

Each example level was carried out as described below under theconditions indicated in Table 1.

The film was loaded into a vacuum chamber and the chamber was vacuumedup to 1.5×10⁻⁴ Pa. Next, after introduction of oxygen, argon wasintroduced as an inert gas to adjust the total pressure to 0.5 Pa.

Power was applied on a sintered indium-tin composite oxide target or asintered indium oxide target not containing tin oxide at a power densityof 2 W/cm² to form a transparent conductive film by a DC magnetronsputtering method. The film thickness was controlled by changing thespeed of the film when the film passed over the target. The ratio of thepartial pressure of water to the partial pressure of the inert gas inthe atmosphere during sputtering was measured with use of a gas analyzer(Transpector XPR3, manufactured by INFICON Co., Ltd.). For the purposeof adjusting, in each example level, the ratio of the partial pressureof water to the partial pressure of the inert gas in the atmosphereduring sputtering, adjustment was performed, as indicated in Table 1,for the introduction amount of water or hydrogen atom-containing gas andthe temperature of the heating medium in the temperature controller thatcontrolled the temperature of the center roll with which the film ran incontact. In the example levels that employed the above-described method[3] of finely accurately controlling the change in the ratio of thepartial pressure of water to the partial pressure of the inert gas inthe atmosphere during sputtering from the start to the completion offilm formation, the temperature of the temperature controller waschangeably controlled, and the temperature right in the middle betweenthe maximum value and the minimum value of the temperature from thestart to the completion of film formation was listed as the centralvalue in Table 1.

The film obtained by forming and laminating the transparent conductivefilm was subjected to the heating treatment indicated in Table 1 andthen to the measurement. Table 1 shows the measurement results.

Comparative Example 1 to 7

Transparent conductive films were prepared in the same manner as inExample 1 under the conditions indicated in Table 1 and evaluated. Table1 shows the results.

TABLE 1 Method of Central value Difference between Content of Centralcontrolling of (partial maximum value and tin oxide in temperature(partial pressure pressure of minimum value in Flow of transparent of ofwater/partial water/partial (partial pressure of oxygen/ conductivetemperature Film pressure of pressure of water/partial flow of filmcontroller thickness argon) (*1) argon) pressure of argon) argon (% bymass) (° C.) (nm) Example 1 [1] 1.13 × 10⁻³ 0.5 × 10⁻⁴ 0.055 3 −10 20Example 2 [2] 1.13 × 10⁻³ 0.6 × 10⁻⁴ 0.055 3 −10 20 Example 3 [3] 1.15 ×10⁻³ 0.6 × 10⁻⁴ 0.055 3 10 20 Example 4 [3] 4.10 × 10⁻⁴ 1.0 × 10⁻⁴ 0.0551 5 14 Example 5 [3] 1.30 × 10⁻³ 1.0 × 10⁻⁴ 0.055 10 5 30 Example 6 [3]1.11 × 10⁻³ 0.2 × 10⁻⁴ 0.055 3 −12 20 Example 7 [3] 1.20 × 10⁻³ 1.8 ×10⁻⁴ 0.055 3 7 20 Example 8 [3] 2.92 × 10⁻³ 1.9 × 10⁻⁴ 0.045 1 70 30Example 9 [3] 1.32 × 10⁻³ 1.9 × 10⁻⁴ 0.026 0.5 10 20 Comparative [3]3.80 × 10⁻⁴ 0.5 × 10⁻⁴ 0.046 3 −12 23 Example 1 Comparative [3] 3.10 ×10⁻³ 1.9 × 10⁻⁴ 0.055 3 −12 20 Example 2 Comparative [3] 1.15 × 10⁻³ 0.6× 10⁻⁴ 0.055 11 −10 20 Example 3 Comparative [3] 1.15 × 10⁻³ 0.8 × 10⁻⁴0.055 3 10 8 Example 4 Comparative None 2.68 × 10⁻³ 6.0 × 10⁻⁴ 0.055 1−10 20 Example 5 Comparative [3] 1.12 × 10⁻³ 0.8 × 10⁻⁴ 0.055 3 5 32Example 6 Comparative [3] 3.25 × 10⁻⁴ 0.8 × 10⁻⁴ 0.025 0 −12 25 Example7 Value of normalized integrated intensity of Flexi- Conditions Totallight Surface diffraction peak Crystal bility of heating transmittanceresistance in (222) plane grain size Pen sliding test treatment (%)(Ω/□) (cps · °/nm) (nm) durability test (mm) Example 1 165° C. 87.5 57615.32 230 Transparent at sliding 14.8 75 min portion On-resistance 0.2kΩ Example 2 165° C. 87.4 587 14.52 220 Transparent at sliding 14.8 75min portion On-resistance 0.2 kΩ Example 3 165° C. 87.3 609 11.91 50Transparent at sliding 11.5 75 min portion On-resistance 0.2 kΩ Example4 180° C. 88.2 870 5.98 80 Transparent at sliding 12.0 75 min portionOn-resistance 0.2 kΩ Example 5 150° C. 86.7 450 13.24 70 Transparent atsliding 15.4 60 min portion On-resistance 0.2 kΩ Example 6 165° C. 87.6653 22.81 110 Transparent at sliding 15.2 75 min portion On-resistance0.2 kΩ Example 7 165° C. 87.1 562 4.28 40 Transparent at sliding 10.7 75min portion On-resistance 0.2 kΩ Example 8 165° C. 85.9 720 4.02 30Transparent at sliding 13.8 75 min portion On-resistance 0.2 kΩ Example9 165° C. 86.8 675 18.52 900 Transparent at sliding 15.2 75 min portionOn-resistance 0.2 kΩ Comparative 150° C. 87.4 528 27.62 200 Transparentat sliding 16.0 Example 1 30 min portion On-resistance 0.2 kΩComparative 165° C. 86.3 620 0 No crystal Sliding portion whitened 10.1Example 2 75 min grain On-resistance 900 kΩ Comparative 165° C. 86.5 4600.21 10 Sliding portion whitened 10.1 Example 3 75 min On-resistance 900kΩ Comparative 165° C. 88.6 1050 0 No crystal Sliding portion whitened9.0 Example 4 75 min grain On-resistance 900 kΩ Comparative 165° C. 86.4734 0.83 8 Sliding portion whitened 10.0 Example 5 75 min On-resistance900 kΩ Comparative 165° C. 86.9 350 34.12 340 Transparent at sliding22.0 Example 6 75 min portion On-resistance 0.2 kΩ Comparative 165° C.86.3 680 52.22 1100 Transparent at sliding 22.3 Example 7 75 min portionOn-resistance 0.2 kΩ (*1) “Methods of controlling partial pressure ofwater/partial pressure of argon” [1] to [3] [1]: Method of controllingintroduction of water by a mass flow controller [2] Method ofcontrolling introduction of a hydrogen atom-containing gas by a massflow controller (a hydrogen gas is used in the example) [3]: Method ofcontrol by temperature of a center roll via a temperature controller

As indicated in Table 1, the transparent conductive films in Examples 1to 9 are excellent in pen sliding durability and flexibility, thushaving both characteristics in combination. In Comparative Examples 1 to7, however, either the pen sliding durability or the flexibility cannotbe attained.

INDUSTRIAL APPLICABILITY

As described above, a transparent conductive film excellent in pensliding durability and flexibility can be prepared according to thepresent invention. The transparent conductive film is very useful forapplication such as a resistive film type touch panel.

REFERENCE SIGNS LIST

-   -   1. Film    -   2. Center roll    -   3. Chimney    -   4. Indium-tin composite oxide target

The invention claimed is:
 1. A transparent conductive film comprising atransparent plastic film substrate and an indium-tin composite oxidetransparent conductive film laminated on at least one surface of thetransparent plastic film substrate, wherein the indium-tin compositeoxide transparent conductive film is a semi crystalline state, thetransparent plastic film substrate is coated with a curable resin layer,and the indium-tin composite oxide transparent conductive film islaminated on the curable resin layer, and a value of normalizedintegrated intensity of a diffraction peak measured by X-raydiffractometry in a (222) plane due to a crystal of the indium-tincomposite oxide transparent conductive film being 4 to 25 cps⋅°/nm, thevalue of normalized integrated intensity of the diffraction peakmeasured by X-ray diffractometry in a (222) plane due to a crystal ofthe indium-tin composite oxide transparent conductive film is measuredas follows, the measurement is performed with use of a samplehorizontally-holding X-ray diffractometer for thin film evaluation as anX-ray diffractometer, a parallel beam optical system including amultilayer film mirror is used, and a CuKα ray with a wavelength of1.54186 angstroms is used as a light source with an output of 40 kV and30 mA, used as an incidence-end slit system is a soller slit (5.0°), anincident slit (0.2 mm), and a longitudinal control slit (10 mm), andused as a receiving-end slit is a parallel slit analyzer (0.114 deg), a20 mm square sample is fixed to a stage with double sided tape or fixedby suction with use of a porous suction sample holder, the measurementis performed at an incident angle of the X-ray of 0.25°, with ascintillation counter detector scanned in an out-of-plane direction, andat a step interval of 0.02° and a measurement speed of 2.0°/min, adiffraction line from the (222) plane of the indium-tin composite oxidetransparent conductive film appears at a position of about 30.5° (2θ) asa peak when the CuKα ray is used, background subtraction is performedaccording to the Sonneveld-Visser method and the integrated intensity ofa diffraction peak in the (222) plane is calculated, and a valueobtained by dividing the integrated intensity by the thickness of theindium-tin composite oxide transparent conductive film is defined as thevalue of normalized integrated intensity of the diffraction peak in the(222) plane.
 2. The transparent conductive film according to claim 1,wherein the indium-tin composite oxide transparent conductive film has acrystal grain size of 10 to 1000 nm.
 3. The transparent conductive filmaccording to claim 1, wherein the indium-tin composite oxide transparentconductive film includes 0.5 to 10% by mass of tin oxide.
 4. Thetransparent conductive film according to claim 1, wherein the indium-tincomposite oxide transparent conductive film has a thickness of 10 to 30nm.
 5. The transparent conductive film according to claim 1, wherein thecurable resin layer contains a curable resin and a resin non-compatiblewith the curable resin.